Frontier Molecular Orbital Contributions to Chlorination versus Hydroxylation Selectivity in the Non-Heme Iron Halogenase SyrB2

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F17%3A00471846" target="_blank" >RIV/61388955:_____/17:00471846 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/jacs.6b11995" target="_blank" >http://dx.doi.org/10.1021/jacs.6b11995</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.6b11995" target="_blank" >10.1021/jacs.6b11995</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Frontier Molecular Orbital Contributions to Chlorination versus Hydroxylation Selectivity in the Non-Heme Iron Halogenase SyrB2

Popis výsledku v původním jazyce

The ability of an Fe-IV=O intermediate in SyrB2 to perform chlorination versus hydroxylation was computationally evaluated for different substrates that had been Studied experimentally. The pi-trajectory for H atom abstraction (Fe-IV=O oriented perpendicular to the C-H bond of substrate) was found to lead to the S = 2 five-coordinate HO-Fe-III-Cl complex with the C-center dot of the substrate, pi-oriented relative to both the Cl- and the OH- ligands. From this ferric intermediate, hydroxylation is thermodynamically faVored, but chlorination is intrinsically more reactive due to the energy splitting between two key redox-active d pi* frontier Molecular orbitals (FMOs). The splitting is determined by the differential ligand field effect of Cl- OH- versus on the Fe center. This makes chlorination effectively competitive with hydroxylation. Chlorination versus hydroxylation selectivity is then determined by the orientation of the substrate with respect to the HO-Fe-Cl plane that controls either the Cl- or the OH- to rebound depending on the relative pi-overlap with the substrate C radical. The differential contribution of the two FMOs to chlorination versus hydroxylation selectivity in SyrB2 is related to reaction mechanism that involves two asynchronous transfers: electron transfer from the substrate radical to the iron center followed by late ligand (Cl- or OH-) transfer to the substrate.

Název v anglickém jazyce

Frontier Molecular Orbital Contributions to Chlorination versus Hydroxylation Selectivity in the Non-Heme Iron Halogenase SyrB2

Popis výsledku anglicky

The ability of an Fe-IV=O intermediate in SyrB2 to perform chlorination versus hydroxylation was computationally evaluated for different substrates that had been Studied experimentally. The pi-trajectory for H atom abstraction (Fe-IV=O oriented perpendicular to the C-H bond of substrate) was found to lead to the S = 2 five-coordinate HO-Fe-III-Cl complex with the C-center dot of the substrate, pi-oriented relative to both the Cl- and the OH- ligands. From this ferric intermediate, hydroxylation is thermodynamically faVored, but chlorination is intrinsically more reactive due to the energy splitting between two key redox-active d pi* frontier Molecular orbitals (FMOs). The splitting is determined by the differential ligand field effect of Cl- OH- versus on the Fe center. This makes chlorination effectively competitive with hydroxylation. Chlorination versus hydroxylation selectivity is then determined by the orientation of the substrate with respect to the HO-Fe-Cl plane that controls either the Cl- or the OH- to rebound depending on the relative pi-overlap with the substrate C radical. The differential contribution of the two FMOs to chlorination versus hydroxylation selectivity in SyrB2 is related to reaction mechanism that involves two asynchronous transfers: electron transfer from the substrate radical to the iron center followed by late ligand (Cl- or OH-) transfer to the substrate.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GJ15-10279Y" target="_blank" >GJ15-10279Y: Redoxní vlastnosti a reaktivita nehemových aktivních center se železem</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

—

Svazek periodika

139

Číslo periodika v rámci svazku

6

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

2396-2407

Kód UT WoS článku

000394482200042

EID výsledku v databázi Scopus

2-s2.0-85013059462